Mouldable and extrudable polyether-ester-amide block copolymers

ABSTRACT

The invention relates to a method of preparing polyether-ester-amide block copolymers having recurrent units of the general formula: ##STR1## wherein A is a polyamide sequence and B a linear or branched polyoxyalkylene glycol sequence, the alkylene radical of which comprises at least two carbon atoms, and wherein n indicates that there is a great number of recurrent units. The plastic materials prepared by the novel method have mechanical properties which allow them to be used in technological transformation operations for the manufacture or moulded or extruded articles such as films, sheaths, fibres for textiles products, etc.. They may also be used for making bonded or welded linings. The novel method comprises reacting in the fused state at an elevated temperature and under high vacuum a dicarboxylic polyamide, the COOH groups of which are located at the chain ends, with a polyoxyalkylene glycol hydroxylated at the chain ends, in the presence of a catalyst constituted by a tetraalkylorthotitanate having the general formula Ti(OR) 4 , wherein R is a linear or branched aliphatic hydrocarbon radical having 1 to 24 carbon atoms, such a methyl, isopropyl, butyl, ethylhexyl, dodecyl, hexadodecyl.

This is a continuation of application Ser. No. 948,297 filed Oct. 3,1978, now U.S. Pat. No. 4,230,838, which in turn is a continuation ofapplication Ser. No. 784,723, filed Apr. 5, 1977, now abandoned which isin turn a continuation of application Ser. No. 582,428, filed May 30,1975, now abandoned.

The instant invention relates to a method of preparing mouldable and/orextrudable polyether-ester-amide block copolymers having recurrent unitsof the general formula: ##STR2## wherein A is a polyamide sequence and Ba linear or branched polyoxyalkylene glycol sequence, the alkyleneradical of which comprises at least two carbon atoms, and wherein nindicates that there is a great number of recurrent units.

Polymers of this type have already been prepared by synthesis and usedas anti-static additives in the field of spinning and weaving polyamideor polyester fibres with a view to avoid the building-up of electriccharges. The French Pat. Nos. 1,444,437 and 2,178,205 disclose methodswhich comprise reacting a dicarboxylic polyamide with a polyoxyalkyleneglycol for obtaining block polycondensates used as anti-static agents;however, the products obtained by these known methods do not exhibitsufficiently satisfactory properties which will permit them to be usedalone in moulding or extruding operations and, are therefore only usedas additives.

The instant invention is aimed at overcoming these drawbacks, and theobject of the invention is to provide a method of preparingpolyether-ester-amide block copolymers having mechanical propertieswhich allow these plastic materials to be used in technologicaltransformation operations for the manufacture of moulded or extrudedarticles such as films, sheaths, fibres for textile products, etc..These products may also be used for making bonded or welded linings.

The method of preparing polyether-ester-amide block copolymers inaccordance with the instant invention comprises reacting in the fusedstate at an elevated temperature and under high vacuum a dicarboxylicpolyamide, the COOH groups of which are located at the chain ends, witha polyoxyalkylene glycol hydroxylated at the chain ends, in the presenceof a catalyst constituted by a tetraalkylorthotitanate having thegeneral formula Ti(OR)₄, wherein R is a linear or branched aliphatichydrocarbon radical having 1 to 24 carbon atoms, such a methyl,isopropyl, butyl, ethylhexyl, dodecyl, hexadodecyl.

The action of this catalyst brings along a great number of advantages asregards the polycondensation reaction as well as the properties of theproduct thus obtained.

At the beginning of the reaction two non-miscible phases are present,one of which is the polyamide phase which exhibits a comparatively lowfluidity. In the absence of the above-mentioned catalyst thepolycondensation reaction will be quite incomplete, the viscosity valueswill remain small and the product obtained will contain a great amountof polyoxyalkylene glycol which has not reacted, whereby the productobtained is rendered friable and unable to undergo the technologicaltransformation operations such as moulding, calendering, extrusion, andthe like.

When applying the method according to the invention, wherein thepolycondensation reaction is effected in the fluid state in the presenceof a tetraalkylorthotitanate, a product is obtained which hassatisfactory mechanical properties and which, consequently, can besubmitted to transformation processes such as moulding or extrusion witha view to manufacturing the desired finished products.

The catalyst may be used alone or in combination with an alkaline oralkaline-earth alcoholate in an amount of 0.01 to 5% by weight,preferably 0.05 to 2% by weight of the total amount of the reactionmixture constituted e.g. by Ti(OR)₄ +RoNa.

The polyamides having dicarboxylic chain ends are obtained byconventional methods currently used for preparing such polyamides, suchmethods comprising e.g. the polycondensation of a lactam or thepolycondensation of an amino-acid or of a diacid and a diamine, thesepolycondensation reactions being carried out in the presence of anexcess amount of an organic diacid the carboxylic groups of which arepreferably located at the ends of the hydrocarbon chain; thesecarboxylic diacids are fixed during the polycondensation reaction so asto form constituents of the macro-molecular polyamide chain, and theyare attached more particularly to the ends of this chain, which allows aα-ω-dicarboxylic polyamide to be obtained. Furthermore, this diacid actsas a chain limitator. For this reason, an excess amount ofα-ω-dicarboxylic diacid is used with respect to the amount necessary forobtaining the dicarboxylic polyamide, and by conveniently selecting themagnitude of this excess amount the length of the macromolecular chainand consequently the average molecular weight of the polyamides may becontrolled.

The polyamide can be obtained starting from lactams or amino-acids thehydrocarbon chain of which comprises from 4 to 14 carbon atoms, such ascaprolactam, oenantholactam, dodecalactam, undecanolactam,dodecanolactam, 11-amino-undecanoic acid, or 12-aminododecanoic acid.

The polyamide may also be a product of the condensation of adicarboxylic acid and a diamine such as nylon 6-6, 6-9, 6-10, 6-12 and9-6, which are products of the condensation of hexamethylene diaminewith adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid,and of nonamethylene diamine with adipic acid.

The diacids used as chain limitators in the reaction of synthesis of thepolyamide, which also allow polyamides having carboxyl chain ends, to beobtained, are carboxylic diacids, preferably aliphatic carboxylicdiacids having 4 to 20 carbon atoms, such as succinic acid, adipic acid,suberic acid, azelaic acid, sebacic acid, undecanedioic acid anddodecanedioic acid.

Diacids of the cycloaliphatic or aromatic type may also be used. Theyare used in excess amounts in the proportion required for obtaining apolyamide having the desired average molecular weight, in accordancewith conventional calculations such as currently used in the field ofpolycondensation reactions. The average molecular weight of thedicarboxylic polyamides is comprised between 300 and 15000, andpreferably between 800 and 5000.

The polyethers having hydroxyl chain ends are linear or branchedpolyoxyalkylene gylcols such as polyoxyethylene glycol, polyoxypropyleneglycol, polyoxytetramethylene glycol or mixtures thereof, or acopolyether derived from the above mentioned compounds, the averagemolecular weight of said polyethers being comprised between 200 and6000, preferably between 400 and 3000.

The proportion by weight of polyoxyalkylene glycol with respect to thetotal weight of the constituents may vary from 5 to 85% and ispreferably comprised between 10 and 50%. The polycondensation reactionfor preparing a polyether-ester-amide is carried out in the presence ofthe catalyst under stirring and under a high vacuum on the order of 0.05to 5 mm Hg at temperatures above the melting points of the constituentsused, said temperatures being selected so that the reacting constituentsare maintained in the fluid state; these temperatures are comprisedbetween 100° and 400° C., and preferably between 200° and 300° C.

The reaction time may vary from 10 minutes to 10 hours, and ispreferably comprised between 1 hour and 7 hours.

The reaction time depends on the nature of the polyoxyalkylene glycol,and it must be sufficiently long to allow the final viscosity to beobtained which is required for the obtention of products havingsatisfactory properties such as required for mouldable and/or extrudableplastic materials.

It should be noted, however, that preferably an equimolar ratio shouldexist between the carboxylic groups and the hydroxyl groups, so that thepolycondensation reaction takes place under optimum conditions with aview to obtaining the desired product.

Additives such as anti-oxidants, stabilizing agents against the effectsof light and heat, fire-proofing agents and pigments may be added to thepolycondensate prior to the transformation operations or, when possible,during the polycondensation reaction, with a view to improving theproperties of the final product or to modifying its properties,depending on the particular application envisaged.

The testing and identification values of the products obtained are asfollows:

The Vicat point in °C. is determined in accordance with ASTM standard D1525 65T.

The intrinsec viscosity is measured in metacresol at 25° C. (initialconcentration: 0.8 g per 100 ml).

Elongation under tension is measured in accordance with ASTM standard D638 67T, and the torsional modulus is measured in accordance with ASTMstandard D 1043 61T (according to the CLASH and BERG method).

The invention will be described hereinafter by means of several exampleswhich are given by way of illustration but not of limitation.

EXAMPLE 1

310 grs. 11-dicarboxylic polyamide having an average molecular weight of2000, which had previously been prepared by polycondensation of11-aminoundecanoic acid in the presence of adipic acid was introducedinto a reactor having a capacity of 1 liter. 146 grs. polyoxyethyleneglycol having a average molecular weight of 1000 and 1.5 grs.tetrabutylorthotitanate was then added. The reactive mixture was placedunder an inert atmosphere and heated to a temperature of 260° C.; avacuum was then produced in the reactor, while the mixture wasvigorously stirred from the moment at which the constituents melted. Thereaction was carried on during 7 hours at 260° C. under a vacuum of 0.1mm Hg, and the stirring velocity had to be reduced as the viscosityincreased.

The product obtained had an intrinsic viscosity of η=1.2; differentialthermal analysis and thermo-mechanical analysis showed that the meltingpoint of the product was 173° C.; it presents a first glass transitionpoint at -58° C., and another one at -18° C.

A portion of the product was finely ground to produce a powder having aparticle size lower than 0.1 mm; 20 grs. of this powder was extractedwith benzene during 24 hours in a Kumagawa extractor. 0.38 grs.polyoxyalkylene glycol which had not reacted was thus recovered, whichcorresponded to a consumption of at least 95% of the total amount ofpolyethylene glycol initially used.

The product was then extruded by means of a BRABENDER extruder at 210°C. and at a speed of 30 rpm. At the outlet of the extruder the productwas obtained in the form of a string or rod which was cut into smallcylinders which were melted by heating so as to allow them to beinjection-moulded by means of an ARBURG injection moulding machine.

Test specimens having a thickness of 2 mm and a thinned section of alength of 50 mm were submitted to tension tests at a temperature of 20°C. at a speed of 14 mm per minute. According to ASTM standard D 638 67Ttensional elongation was 14% under a stress of 97 kg/sq.cm at the yieldpoint, and 560% under a stress of 280 kg/sq.cm at rupture.

The values of the torsional modulus G (according to the method of CLASH& BERG, ASTM specification No. D 1043 61T) were as follows for thevarious temperatures indicated:

    ______________________________________                                        T °C.                                                                             -40° C.                                                                         -20° C.                                                                         0° C.                                                                       20° C.                                                                       40° C.                         G(kg/sq.cm):                                                                             1040     740      560  510   500                                   ______________________________________                                    

The Vicat point was 151° C. under a load of 1 kg with a heating rate of50° C. per hour.

EXAMPLE 2

For the purpose of comparison the same procedure as the one described inExample 1 was applied, but without using a catalyst, whereas all theother conditions were identical.

The product obtained had an intrinsic viscosity of 0.4 as measured inm-cresol at 25° C. Only 65% of the polyoxyethylene glycol was consumedin the reaction.

No technological quality control test could be carried out on thisproduct, as the latter was too friable.

EXAMPLE 3

Using a mode of operation similar to the one described in Example 1herein-above, 88.3 grs. 11-dicarboxylic polyamide (obtained bypolycondensation of 11-amino-undecanoic acid in the presence of adipicacid) having an average molecular weight of 3200 was reacted with 11.7grs. polyoxyethylene glycol having an average molecular weight of 425 inthe presence of 0.28 gr. tetrabutylorthotitanate during 5 hours at 280°C. under high vacuum.

A block polycondensate was obtained which contained 11.7% (by weight)recurrent polyoxyethylene glycol units in the combined state in themacro-molecule. The entire amount of the polyoxyethylene glycolinitially used was consumed during the polycondensation reaction and theproduct obtained contained no free polyoxyethylene glycol.

The product obtained had an intrinsic viscosity of 0.80, a Vicat pointof 163° C. (at 0° C. under a load of 1 kg) and a melting point of 180°C.

Elongation under tension was 14% under a stress of 183 kg/cm² at theyield point, and 375% under a stress of 367 kg/cm² at rupture. Thevalues of the torsional modulus G measured in accordance with the methodof CLASH and BERG were as follows for the temperatures indicated:

    ______________________________________                                        T °C.:                                                                         -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       40° C.                                                                       60° C.                      G(kg/cm.sup.2):                                                                       4127     2510     1222 755   614   437                                ______________________________________                                    

EXAMPLE 4

Using the mode of operation described in Example 1, herein-above, 25.1grs. 11-dicarboxylic polyamide (obtained by polycondensation of11-amino-undecanoic acid in the presence of adipic acid) having anaverage molecular weight of 810 was reacted with 74.9 grs.polyoxyethylene glycol having an average molecular weight of 2400 in thepresence of 0.46 gr tetrabutylorthotitanate.

The reaction was carried out at 280° C. under high vacuum during 4hours.

The melting point of the obtained polymer was 140° C.

Its intrinsic viscosity was 1.15 and the block polycondensate contained75.1% by weight polyethylene glycol in the combined state.

EXAMPLE 5

The catalyst constituted by tetrabutylorthotitanate doped with sodium(catalyst a) was prepared in an anhydrous medium by dissolving 1 gr.sodium in 99 grs. n-butanol and then adding 14.8 grs.tetrabutylorthotitanate. The solution was then diluted with n-butanol toa total volume of 200 ml.

Using the mode of operation described in Example 1, 54 grs.11-dicarboxylic polyamide having an average molecular weight of 1135 wasreacted with 46 grs. polyoxyethylene glycol having an average molecularweight of 970 in the presence of 1.46 grs. tetrabutylorthotitanate dopedwith sodium (catalyst a) during 4 hours at 280° C. under high vacuum.The product obtained had an intrinsic viscosity of 1.68 and contained47.9% (by weight) polyoxyethylene glycol in the combined state in thepolycondensate, the melting point of which was 150° C. The Vicat pointwas 125° C. under a load of 1 kg.

Elongation under tension was 15% under a stress of 68 kg/cm² at theyield point, and 310% under a stress of 165 kg/cm² at rupture. Thevalues of the torsional modulus G determined according to the method ofCLASH & BERG were as follows for the temperatures indicated:

    ______________________________________                                        T °C.:                                                                            -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       60° C.                         G(kg/cm.sup.2):                                                                          464      314      240  273   160                                   ______________________________________                                    

EXAMPLE 6

The catalyst constituted by tetrabutyl-orthotitanate doped withmagnesium (catalyst b) was prepared in an anhydrous medium by dissolving1.41 gr. magnesium turnings in 300 ml of anhydrous n-butanol. Thesolution was heated under reflux during 4 hours, and 36 grs.tetrabutyl-orthotitanate was then added, followed by heating underreflux during 1 hour. The resulting mixture was then cooled andprotected against humidity.

In accordance with the mode of operation described in Example 1herein-above, 77.4 grs. 11-dicarboxylic polyamide having an averagemolecular weight of 3420 was reacted with 22.6 grs. of apolyoxypropylene having an average molecular weight of 1000, in thepresence of 0.67 gr. tetrabutylorthotitanate doped with magnesium,during 4 hours at 280° C. under high vacuum.

The product obtained had an intrinsic viscosity of 1.5 and contained25.5% by weight polyoxypropylene glycol in the combined state in thepolycondenstate the melting point of which was 175° C. The Vicat pointwas 163° C.

Elongation under tension was 14% under a stress of 162 kg/cm² at theyield point, and 310% under a stress of 324 kg/cm² at rupture.

The values of the torsional modulus G measured according to the methodof CLASH & BERG were as follows for the temperatures indicated:

    ______________________________________                                        T °C.:                                                                         -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       40° C.                                                                       60° C.                      G(kg/cm.sup.2):                                                                       2579     1547     884  554   408   302                                ______________________________________                                    

EXAMPLE 7

Using the same mode of operation as in Example 1 herein-above, 50.7 grs.11-dicarboxylic polyamide having an average molecular weight of 1035 wasreacted with 49.3 grs. polyoxylene glycol having an average molecularweight of 1000 in the presence of 1.51 gr catalyst a(tetrabutylorthotitanate doped with sodium) during 6 hours at 280° C.under high vacuum.

The product obtained contained 55.4% by weight polyoxylene glycol at thecombined state in the polycondensate and had the following properties:

melting point: 157° C.

intrinsic viscosity: 0.90

Vicat point (°C. under a load of 1 kg): 98

Elongation under tension was 18%, under a stress of 54 kg/cm² at theyield point, and 60% under a stress of 64 kg/cm² at rupture.

The values of the torsional modulus G measured according to the methodof CLASH & BERG were as follows for the temperatures indicated:

    ______________________________________                                        T °C.:                                                                            -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       60° C.                         G(kg/cm.sup.2):                                                                          295      151      147  180   120                                   ______________________________________                                    

EXAMPLE 8

In accordance with the mode of operation described in Example 1hereinabove, 75.6 grs. 11-dicarboxylic polyamide having an averagemolecular weight of 3100 was reacted with 24.4 grs.polyoxytetramethylene glycol having an average molecular weight of 1000,in the presence of 0.73 gr. catalyst a (tetrabutyl-orthotitanate dopedwith sodium) during 4 hours at 280° C.

The polycondensate obtained contained 25.2% (by weight)polyoxytetramethylene glycol in the combined state.

The properties were as follows:

melting point: 180° C.

intrinsic viscosity: 1.10

Vicat point (°C. under a load of 1 kg): 163° C.

Elongation under tension was 18% under a stress of 137 kg/cm² at theyield point, and 327% under a stress of 227 kg/cm² at rupture.

The values of the torsional modulus G (CLASH & BERG) were as follows forthe temperatures indicated:

    ______________________________________                                        T °C.:                                                                            -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       60° C.                         G(kg/cm.sup.2):                                                                          2650     1600     1000 825   400                                   ______________________________________                                    

EXAMPLE 9

In accordance with the mode of operation described in Example 1,herein-above, 51.7 grs. 11-dicarboxylic polyamide having an averagemolecular weight of 1000 was reacted with 48.3 grs.polyoxytetramethylene glycol having an average molecular weight of 1000in the presence of 1.45 gr. catalyst a (tetrabutyl-orthotitanate dopedwith sodium) during 6 hours at 280° C. under high vacuum. The blockcopolymer obtained contained 52.9% by weight polyoxytetramethyleneglycol in the combined state.

The properties were as follows:

melting point: 165° C.

intrinsic viscosity: 1.44

Vicat point (°C. under a load of 1 kg): 115° C.

elongation under tension was 18% under a stress of 54 kg/cm² at theyield point, and 647% under a stress of 118 kg/cm² at rupture.

The values of the torsional modulus G (CLASH & BERG) were as follows forthe temperatures indicated:

    ______________________________________                                        T °C.:                                                                         -40° C.                                                                         -20° C.                                                                         0° C.                                                                       22° C.                                                                       40° C.                                                                       60° C.                      G(kg/cm.sup.2):                                                                       773      364      299  238   182   131                                ______________________________________                                    

EXAMPLE 10

25 grs. 12-aminododecanoic acid were introduced into a reactorcomprising an agitator and means for connecting the reactor to a vacuumsource. The acid was heated during 3 hours at a temperature comprisedbetween 220° and 240° C. under reduced pressure, and thepolycondensation was limited by adding 4 grs. adipic acid. Adicarboxylic polyamide having an average molecular weight of 1084 wasthus obtained; the same carboxylic dipolyamide may also be obtained byhydrolytic polymerisation of lactam 12 under pressure at a temperatureof 300° C. in the presence of adipic acid.

27.9 grs. polytetramethylene glycol having an average molecular weightof 1000 was added to 24.7 grs. of the above-mention dicarboxylicdipolyamide in the presence of 0.68 gr. tetrabutyl-orthotitanate.

The reactive mixture was heated in an inert atmosphere until atemperature of 280° C. was reached.

The mixture was then placed under high vacuum (0.1 mm Hg) and thereaction was continued during 3 hours under stirring.

The obtained product had an intrinsic viscosity of 1.3 and contained48.16% (by weight) polyoxytetramethylene glycol in the combined state inthe polycondensate.

EXAMPLE 11

Using the mode of operation similar to the one described in Example 1,herein-above, 68 grs. 11-dicarboxylic polyamide (obtained bypolycondensation of 11-amino-undecanoic acid in the presence of adipicacid) having an average molecular weight of 2000 was reacted with 32grs. polyoxyethylene gycol having an average molecular weight of 1000 inthe presence of 0.33 gr. tetra-isopropyl-orthotitanate during 7 hours at260° C. under high vacuum.

A block polycondensate was obtained which has an intrinsic viscosity of1.2 and contained 33% (by weight) recurrent polyethylene glycol units inthe combined state in the molecule, while the melting point of theproduct obtained was 173° C.

EXAMPLE 12

310 grs. of the dicarboxylic polyamide used in Example 11 and 152 grs.copolyethylene glycol-polypropylene glycol (50/50) having an averagemolecular weight of 1000 were introduced together with 1.3 gr.tetraisopropyl-orthotitanate into a reactor having a capacity of 1 l.

The reaction was carried out under the same conditions as thosedescribed in Example 1. The obtained product had an intrinsic viscosityof 1.4, and the yield was 96% with respect to the consumption ofcopolyoxyalkylene glycol.

EXAMPLE 13

48.3 grs. dihexylammonium azelaate salt (F=151°-152° C.) and 3.35 grs.adipic acid were introduced into a reactor comprising an agitator andmeans for connection with a vacuum source. The reactive mixture washeated to a temperature of 180° C. during 3 hours and to a temperaturecomprised between 180° C. and 250° C. during 2 hours. A 6.9 dicarboxylicpolyamide having an average molecular weight of 1886 was obtained.

17.6 grs. polyoxytetramethylene glycol having an average molecularweight of 1000 was added to 32 grs. of this dicarboxylic polyamide inthe presence of 0.51 gr. tetrabutyl-orthotitanate. The reactive mixturewas placed in an inert atmosphere and heated until a temperature of 280°C. was reached; the mixture was then placed under high vacuum (0.1 mmHg), and the reaction was continued during 2 hours under stirring.

The product obtained had an intrinsic viscosity of 2.05 and contained36.5% by weight polyoxytetramethylene glycol in the combined state inthe polycondensate. Its melting point was 148° C.

EXAMPLE 14

273 grs. dihexylammonium sebacate salt (F=172°-173° C.) and 19.06 grs.adipic acid was introduced into a reactor comprising an agitator andmeans for connection to a vacuum source; the mixture was heated to atemperature comprised between 200° and 220° C. during 4 hours. A6.10-dicarboxylic polyamide having an average molecular weight of 1332was thus obtained. 230 grs. polyoxytetramethylene glycol having anaverage molecular weight of 1000 was added to 306 grs. of thisdicarboxylic polyamide in the presence of 1.5 gr.tetrabutyl-orthotitanate.

The reactive mixture was placed under an inert atmosphere and heateduntil a temperature of 280° C. was reached; the mixture was then placedunder high vacuum (0.1 mm Hg) and the reaction was continued understirring during 3 hours.

The product obtained had an intrinsic viscosity of 1.40 and contained46.93% by weight tetra-oxymethylene glycol in the combined state in thepolycondensate.

Its melting point was 170° C.

EXAMPLE 15

100 grs. hexyldiammonium dodecanoic salt (F=160° C.) and 7.1 grs. adipicacid were introduced into a reactor provided with an agitator and withmeans for connection to a vacuum source, and the mixture was heatedduring 3 hours to 170° C., and then heated during 2 hours to atemperature comprised between 180° C. and 250° C.

A 6.12-dicarboxylic polyamide having an average molecular weight of 1998was thus obtained. 15.5 grs. polytetramethylene glycol having an averagemolecular weight of 1000 was added to 131 grs. of this dicarboxylicpolyamide in the presence of 0.52 gr. tetrabutyl-orthotitanate. Thereactive mixture was placed in an inert atmosphere and heated until atemperature of 280° C. was reached; the mixture was then placed underhigh vacuum (0.1 mm Hg) and the reaction was continued during 3 hoursunder stirring.

The product thus obtained had an intrinsic viscosity of 1.56 andcontained 32.2% (by weight) polyoxytetramethylene glycol in the combinedstate in the polycondensate.

Its melting point was 159° C.

EXAMPLE 16

865 grs. 6-dicarboxylic polyamide having an average molecular weight of1400 and still containing 3.6% (by weight) caprolactam, and 400 grs.polytetramethylene glycol having an average molecular weight of 650 wereintroduced together with 6.4 grs. tetrabutyl-orthotitanate into areactor provided with agitating means and with means for connection witha vacuum source. A partial vacuum was established with a view toeliminating the gases from the reactive medium. The reactive mixture washeated to 240° C. during one hour. When this temperature was reached, avacuum of 1 mm Hg was established and the polycondensation reaction wascontinued for 2 hours, during which period of time the temperatureincreased so as to reach 255° C. The reaction was then discontinued. Theweight of the lactam recovered under vacuum during the reaction was 29grs. The product obtained contained 5.3% substances having a lowmolecular weight which were extracted with benzene, and it had thefollowing properties:

intrinsic viscosity: 1.45

Vicat point: 162° C. under a load of 1 kg

Elongation under tension was 12.5% under a stress of 103 kg/sq.cm at theyield point, and 490% under a stress of 425 kg/sq.cm at rupture.

The values of the torsional modulus G were as follows for thetemperatures indicated (as determined according the method of CLASH andBERG):

    ______________________________________                                        T °C.:                                                                             -40     -20       0    20    60                                   G(kg/sq.cm):                                                                              3400    1900    1200  860   530                                   ______________________________________                                    

EXAMPLE 17

Using an operating mode similar to that described in Example 1hereinabove, 560 grs. 12-dicarboxylic polyamide (obtained by thepolycondensation of lactam 12 in the presence of adipic acid) having anaverage molecular weight of 5600 was reacted with 102 grs.polyoxypropylene glycol having an average molecular weight of 1020 inthe presence of 4 grs. tetra-orthobutyltitanate during 6 hours at 250°C. under a vacuum of 0.3 mm Hg in a reactor. A block polycondensate wasobtained which contained 15.4% (by weight) recurrent polyoxypropyleneglycol units in the combined state in the macromolecule. The entireamount of the polyoxypropylene glycol initially used had been consumedduring the polycondensation reaction. The product obtained had thefollowing properties:

intrinsic viscosity: 1.4

Vicat point: 157° C. (under a load of 1 kg)

Softening point: 175° C.

Elongation under tension was 365% under a stress of 375 kg/sq.cm atrupture

The values of the torsional modulus G according to the method of CLASHand BERG were as follows, for the temperatures indicated:

    ______________________________________                                        T °C.:                                                                             -40     -20      0   22   40   60                                 G(kg/sq.cm):                                                                              4600    3300   2400 1700 860  620                                 ______________________________________                                    

It is to be understood that the invention is not limited to the specificexamples described hereinabove which are given only by way ofillustration, and that modifications may be made within the scope of theappended claims without departing from the spirit of the invention.

What is claimed is:
 1. A moldable and extrudable polyether-ester-amideblock copolymer having the formula: ##STR3## wherein A is a linearsaturated aliphatic polyamide sequence formed from a lactam or aminoacid having a hydrocarbon chain containing 4 to 14 carbon atoms or froman aliphatic C₆ -C₁₂ dicarboxylic acid and a C₆ -C₉ diamine, in thepresence of chain-limiting aliphatic carboxylic diacid having 4 to 20carbon atoms; said polyamide sequence having an average molecular weightof between about 300 and about 15000; and B is a polyether sequenceformed from linear or branched aliphatic polyoxyalkylene glycols ormixtures thereof, said polyoxyalkylene glycol having an averagemolecular weight of from about 200 to about 6000; wherein the proportionby weight of polyoxyalkylene glycol with respect to the total weight ofpolyether-ester-amide is from about 5 to about 85%; and n indicates asufficient number of repeating units so that said polyether-ester-amidehas an intrinsic viscosity of from 0.8 to 2.05.
 2. The moldable andextrudable polyether-ester-amide block copolymer as defined in claim 1which exhibits a melting point in the range of from about 140° to about180° C., a Vicat point in the range of from about 98° to about 157° C.and an elongation under tension at yield point in the range of fromabout 12.5% to about 18%.
 3. The moldable and extrudablepolyether-ester-amide copolymer as defined in claim 2 which exhibits atorsional modulus at 0° C. in the range of from about 147 to about 2400kg/cm².
 4. The polyether-ester-amide copolymer of claim 1 wherein thelactam or amino acid having a hydrocarbon chain of 4 to 14 carbon atomsis selected from the group consisting of caprolactam, oenantholactam,dodecalactam, undecanolactam, dodecanolactam, 11-amino-undecanoic acid,and 12-aminododecanoic acid.
 5. The polyether-ester-amide copolymer ofclaim 1 wherein the polyamide is formed from a dicarboxylic acid and adiamine wherein the diamine is hexamethylene diamine or nonamethylenediamine and the acid is adipic acid, azelaic acid, sebacic acid, or1,12-dodecanedioic acid.
 6. The polyether-ester-amide copolymer of claim1 wherein the chain-limiting carboxylic aliphatic diacid is acidselected from the group consisting of succinic acid, adipic acid,suberic acid, azelaic acid, sebacic acid, undecanedioic acid anddodecanedioic acid.
 7. The polyether-ester-amide copolymer of claim 1wherein the polyoxyalkylene glycol is selected from the group consistingof polyoxyethylene glycol, polyoxypropylene glycol,polyoxytetramethylene glycol, mixtures thereof and a copolyether derivedtherefrom.
 8. The polyether-ester-amide copolymer of claim 1 wherein theproportion by weight of polyoxyalkylene glycol is from about 5 to about50%.
 9. The polyether-ester-amide copolymer of claim 8 wherein theproportion by weight of polyoxyalkylene glycol is from about 10 to about50%.
 10. The polyether-ester-amide copolymer of claim 1 wherein thepolyoxyalkylene glycol has an average molecular weight of from about 200to about
 3000. 11. The polyether-ester-amide copolymer of claim 10wherein the polyoxyalkylene glycol has an average molecular weight offrom about 400 to about
 3000. 12. The polyether-ester-amide copolymer ofclaim 10 wherein the polyoxyalkylene glycol has an average molecularweight of from about 200 to about
 400. 13. The polyether-ester-amidecopolymer of claim 1 wherein the polyamide sequence is formed from a11-dicarboxylic polyamide prepared by the polycondensation of11-aminoundecanoic acid and adipic acid and the polyoxyalkylene glycolis polyoxyethylene glycol.
 14. The polyether-ester-amide copolymer ofclaim 13 wherein the average molecular weight of the polyamide sequenceis about 2000 and the average molecular weight of the polyoxyalkyleneglycol is about 1000 and which exhibits an intrinsic viscosity of about1.2, a Vicat point of about 151° C., an elongation under tension atyield point of about 14% and a torsional modulus at 0° C. of about 560kg/cm².
 15. The polyether-ester-amide copolymer of claim 13 wherein theaverage molecular weight of the polyamide sequence is about 3200 and theaverage molecular weight of the polyoxyalkylene glycol is about 425 andwhich exhibits an intrinsic viscosity of about 0.8, a Vicat point ofabout 163° C., an elongation under tension at yield point of about 14%and a torsional modulus at 0° C. of about 1222 kg/cm².
 16. Thepolyether-ester-amide copolymer of claim 13 wherein the averagemolecular weight of the polyamide sequence is about 810 and the averagemolecular weight of the polyoxyalkylene glycol is about 2400 and whichexhibits an intrinsic viscosity of about 1.15 and a melting point ofabout 140° C.
 17. The polyether-ester-amide copolymer of claim 13wherein the average molecular weight of the polyamide sequence is about1135 and the average molecular weight of the polyether sequence is about970 and which exhibits an intrinsic viscosity of about 1.68, a Vicatpoint of about 125° C., an elongation under tension at yield point ofabout 15% and a torsional modulus at 0° C. of about 240 kg/cm².
 18. Thepolyether-ester-amide copolymer of claim 13 wherein the averagemolecular weight of the polyamide sequence is about 1035 and the averagemolecular weight of the polyether sequence is about 1000 and whichexhibits an intrinsic viscosity of about 0.9, a Vicat point of about 98°C., an elongation under tension at yield point of about 18% and atorsional modulus at 0° C. of about 147 kg/cm².
 19. Thepolyether-ester-amide of claim 1 wherein the polyamide sequence isformed by a 11-dicarboxylic polyamide obtained by the condensation of11-aminoundecanoid acid in the presence of adipic acid and thepolyoxyalkylene glycol is copolyoxyethylene polyoxypropylene glycol orpolyoxypropylene glycol.
 20. The polyether-ester-amide copolymer ofclaim 19 wherein the average molecular weight of the polyamide sequenceis about 3420 and the polyether sequence is polyoxypropylene having anaverage molecular weight of about 1000 and which exhibits an intrinsicviscosity of about 1.5, a Vicat point of about 163° C., an elongationunder tension at yield point of about 14% and a torsional modulus at 0°C. of about 884 kg/cm².
 21. The polyether-ester-amide copolymer of claim19 wherein the average molecular weight of the polyamide sequence isabout 2000 and the polyether sequence iscopolyoxyethylene-polyoxypropylene glycol having an average molecularweight of about 1000 and which exhibits an intrinsic viscosity of about1.4.
 22. The polyether-ester-amide copolymer of claim 1 wherein thepolyamide sequence is formed from a 11-dicarboxylic polyamide preparedby the polycondensation of 11-amino decanoic acid in the presence ofadipic acid and the polyoxyalkylene glycol is polyoxytetramethyleneglycol.
 23. The polyether-ester-amide copolymer of claim 22 wherein theaverage molecular weight of the polyamide sequence is about 3100 and theaverage molecular weight of the polyether sequence is about 1000 andwhich exhibits an intrinsic viscosity of about 1.10, a Vicat point ofabout 163° C., an elongation under tension at yield point of about 18%and a torsional modulus at 0° C. of about 1000 kg/cm².
 24. Thepolyether-ester-amide copolymer of claim 22 wherein the averagemolecular weight of the polyamide sequence is about 1000 and the averagemolecular weight of the polyether sequence is about 1000 and whichexhibits an intrinsic viscosity of about 1.44, a Vicat point of about115° C., an elongation under tension at yield point of about 18% and atorsional modulus at 0° C. of about 299 kg/cm².
 25. Thepolyether-ester-amide copolymer of claim 1 wherein the polyamidesequence has an average molecular weight of about 1084 and is a12-dicarboxylic acid polyamide formed by condensation of12-aminododecanoic acid in the presence of adipic acid and thepolyoxyalkylene sequence has an average molecular weight of about 1000and is formed from polyoxytetramethylene glycol and which exhibits anintrinsic viscosity of about 1.3.
 26. The polyether-ester-amidecopolymer of claim 1 wherein the polyamide sequence has an averagemolecular weight of about 1886 and is 6.9-dicarboxylic acid polyamideformed by condensation of dihexylammonium azelaate in the presence ofadipic acid and the polyoxyalkylene sequence has an average molecularweight of about 1000 and is formed from polyoxytetramethylene glycol andwhich exhibits an intrinsic viscosity of about 2.05 and a melting pointof about 148° C.
 27. The polyether-ester-amide copolymer of claim 1wherein the polyamide sequence has an average molecular weight of about1332 and is a 6,10-dicarboxylic acid polyamide formed by condensation ofdihexylammonium sebacate in the presence of adipic acid and thepolyoxyalkylene sequence has an average molecular weight of about 1000and is formed from polyoxytetramethylene glycol and which exhibits anintrinsic viscosity of about 1.40.
 28. The polyether-ester-amidecopolymer of claim 1 wherein the polyamide sequence has an averagemolecular weight of about 1998 and is a 6.12-dicarboxylic acid polyamideformed by condensation of hexyldiammonium dodecanoic salt in thepresence of adipic acid and the polyoxyalkylene sequence has an averagemolecular weight of about 1000 and is formed from polyoxytetramethyleneglycol and which exhibits an intrinsic viscosity of about 1.56.
 29. Thepolyether-ester-amide copolymer of claim 1 wherein the polyamidesequence has an average molecular weight of about 1400 and is a6-dicarboxylic acid polyamide formed by condensation of caprolactam andthe polyoxyalkylene sequence has an average molecular weight of about650 and is formed from polyoxytetramethylene glycol and which exhibitsan intrinsic viscosity of about 1.45, a Vicat point of about 162° C., anelongation under tension at yield point of about 12.5% and a torsionalmodulus at 0° C. of about 1200 kg/cm².
 30. The polyether-ester-amidecopolymer of claim 1 wherein the polyamide sequence has an averagemolecular weight of about 5600 and is a 12-dicarboxylic acid polyamideformed by condensation of 12-lactam in the presence of adipic acid andthe polyoxyalkylene sequence has an average molecular weight of about1020 and is formed from polyoxypropylene glycol and which exhibits anintrinsic viscosity of about 1.4, a Vicat point of about 157° C., and atorsional modulus at 0° C. of about 2400 kg/cm².
 31. A fiber productconsisting essentially of the polyether-ester-amide copolymer ofclaim
 1. 32. A fiber product consisting essentially of thepolyether-ester-amide copolymer of claim
 12. 33. The moldable andextrudable polyether-ester-amide block copolymer of claim 1 formed inthe presence of a titanate-like catalyst.
 34. The moldable andextrudable polyether-ester-amide block copolymer of claim 1 formed inthe presence of a tetra-alkylortho-titanate catalyst.